Process for hydrocarbon oil conversion



Nov. 3, V1936. c. P. DUBBS I 2,059,625

PRocEss FOR HYDROGARBON OIL CONVERSION Filed Jan. 17, 1927 Patented Nov. 3, 1936 UNlTED STATES PATENT OFFICE PROCESS FOR HYDROCARBON OIL CONVERSION Carbon P. Dubbs, Wilmette, Ill., assignor, by mesne assignments, to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Application `lanuary 17, 1927, Serial No. 161,488 11 Claims. (Cl. 19662) The invention relates to a conversion of hy- An apparatus to carry out this invention can drocarbon oils under heat and pressure in the be conceived without difculty by those skilled in presence of a hydrogenating gas, such as hythe art, and any apparatus by which the object drogen, for the purpose of making larger quanof the invention can be carried out is well withtities of lighter hydrocarbons containing high in theA scope of the invention, and I will illuspercentages of saturated hydrocarbons. trate hereinafter a particular method and appa- I am aware that the treatment of hydrocarratus in which this invention can be carried out bon oils with hydrogen or the like has been the without limiting myself to this particular design. subject of considerable development in the prior In the drawing the single figure is a side elelo art, but the processes heretofore used had a relavational view showing schematically and diatively low efficiency and produced only relatively grammatically a suitable form of apparatus.

small amounts of the desired products. Referring to the drawing, oil can be pumped One of the objects of this invention is to imfrom any suitable source, not shown, through line prove the efciency of the process of the treatl and passed through pump 2, line 3 and line 4 l5 ment by subjecting the hydrocarbon oils to a controlled by a valve 5 into the upper portion 5 repeated treatment until the desired products are of a dephlegmator t. The dephlegmator can be obtained in the quantity desired whiley at the same of any suitable design. In the dephlegmator the time the operation of the process is kept within oil is preheated to some extent by the vapors uneicient and economical limits by subjecting the dergoing fractionation therein, and said oil and hydrocarbon oils during each pass of the treatreflux condensate are withdrawn from the bot- 20 ment to a relatively mild action by the hydrogetom of the dephlegmator 1 controlled by valve 8 Hating ageltand passed by means of pump 9 controlled by In ShOIt, the DIOCGSS C0I1SStS 'in Passing h5 valves l0 into main feed line Il. The oil from dI'OCarbOrl Oil thI'Ollgh a treating ZOIle Where t line Il is directed through heating tubes I2 pois heated t0 Com/S1011 temperature under any sitioned in furnace I3 which can be of any suit- 25 pressure desired, then causing separation of the able design and heated in any Suitable manner, heated Oil into vapors and heavy hydf'ocarbon not shown. If desired a portion of the oil can constituents while the vapors are subjected to be passed from line 3 directly inte iine 1 te be further separation into light products and heavier directed inte heating Zones i2 Without passirig condensetes-the condensate cempemg en the through dephlegmator 6. This is effected by con- 30 fraetlees Whleh heve not been Sufelently treat' trolling the opening of valve 5 within line 4 and ed to give the desired product. The light vapors of Vaive i4 on line i5. ae there Condeesed and Collected as a nel prod' The oil is heated in heating coils l2 to proper uct Whe the msufclenmy treated condense'tes temperatures of conversion and passed therefrom gatrnellrllrtned to the beaune Zone for further through transfer line i6 controlled byvvalve Il into reaction chamber i8. According to condiinilof Ugh; iefllelntghggensg SS tions of the operation in the reaction chamber d y vaporization may or may not take place, although rogen, into the material undergoing conversion 1 th rein The Todu t f 40 at any step of the process which will produce the Some. ges maybevo Ytehd e 'f tg C s. 0 40 desired results. A further feature of the invenree'etlen een e W1 Yawn rom. e react-'len tion is to inject said agent or hydrogen preferchamber frem any deemed place e" es ehewn ably into the hydrocarbons which win be subm the dfawmg from the bottom? nigh 1m@ '9 jected to a repeated treatment through the con- Controlled by Valve 2e er by the Stde hue 2' een' version zone, and which will be kept in circula- @Oued by Valve 22' These two' hnes merge mto l45 non therethrough until their transformation into 1111 23 Controlled@ Valve M and loess the Prodthe desired product. This injection can furthercts 0f Teactlon m130 meer Separatuig @hamper more be effected into the hydrocarbons under- 25- The gals 01" Vapofs Separated m Teacton goingtreatment either before or after their pas- Chamber '3 may Dass from the t0p thereof Sage thmughthe heating Zone, according to the through line 26 controlled by valve 21 into line 50 degree of conversion desired. 23 through which they are directed to vapor It is readily seen that there are unlimited num- Separating Chamber 25 With PTOdllCtS 0f reaCtiOn bers of methods to carry out the object of this withdrawn from their places of reaction chamber invention, and I do not wish to limit myself to I8, or these gases and vapors can be directed any one particular apparatus or method, through line 28 controlled by valve 29 directly 55 into the dephlegmator 6 Without passing through vapor separating chamber 25.

Suitable baille means may be used to alter the passage of vapors and to increase the time element of the reaction. In said vapor separating chamber 25 the products of reaction entering through line 23 are separated into heavy liquid portions which accumulate at the bottom thereof and into vapors which are Withdrawn from the top of chamber 25 through line 30 controlled by valve 3i which merges with line 28 to direct the vapors from chamber 25 into the dephlegmator 6. The heavy liquid products of reaction accumulated in the bottom of chamber 25 are drawn off from the bottom or side thereof through lines 32 controlled by valves 33 and evacuated from the process through line 34 controlled by valve 35. In the dephlegmator the vapors are subjected to fractionation and by controlling the temperature at the top of the dephlegmator the suitably desired products are drawn oif from the tcp thereof in the form of vapors through line 36 controlled by valve 31 and pass into condensing means, shown at 38, from Where the liquid condensates and gases are directed into collecting means 39. Collecting means 39 is provided with a gas release line 4l) controlled by valve 4I and liquid draw off e2 controlled by valve 43. If the amount of raw oil fed into the top of dephlegmator E5 through line 4 is insufficient to produce the desired amount of cooling additional cooling can be effected by reserving a portion of the condensate ammumulated in collecting .means 39 through line 44 controlled by valve 45 and pump 46 in line 41.

As a feature of the invention a hydrogenating gas, such as hydrogen, gaseous hydrogenated compounds can be introduced into the oil undergoing treatment at any desired step of the treatment according to the degree of conversion and characteristics of product desired. For instance, hydrogen or the other agents can be Withdrawn from any suitable source, not shown, through line 48 and passed by means of pump 49 into line 5I] controlled by valve 5I and into distributing header 52. From header 52 there are several distributing lines which are connected with various parts of the process, such as line 53 controlled by valve 54 which connects with the discharge of the ravv oil pump 2, also line 55 controlled by valve 56 which connects with the feed line II at the inlet of the heating tubes I2. Also line 51 controlled by valve 58 Which connects the hydrogen or other agent header 52 with the transfer line I6 from which the hot oil is discharged through the heating coil I2. Or a line 59 controlled by valve 60 connects the header 52 With the line I9, and by using this line hydrogen or the other agents used can be -injected into the products of reaction drawn oif from chamber I8.

It can be seen that by controlling the opening of the various valves 54, 56, 58 and 60 and utilizing either one or the other or several of the valves, hydrogen can be introduced in varying proportions at any one or more of the points heretofore described. These connections permit introduction of hydrogen into the liquid hydrocarbons passing rapidly through the system before or after they have received the heat of conversion.

It may be desirable to accomplish the reaction by means of the hydrogen or of any other agent injected in the system into the products of reaction While they are in the vapor form. To this object I have shown a supply line 6I passing into pump 62 through which hydrogen can be injected in the vapors of the process at various points thereof, i. e. by opening valve 63 on line 64 the reacting agent can be injected in the vapors formed in reaction chamber I8 and passing to dephlegmator 6, or by opening valve 65 on line 66 the other reacting agent can be injected into vapors leaving vapor separating chamber 25 before they are introduced into dephlegmator 6, or by opening valve 6'I on line 68 connected to the discharge pump 62 the reacting agent can be introduced into vapors forming the final product of the system.

It is Well understood that I have shown a number of Ways in which and steps of the process at which the reacting agent can be introduced. There are a number of other desirable places in which the reacting agent can be injected, i. e. in the reflux leaving the dephelgmator.

As a further object of the invention, it may be desirable to control the temperature of the reacting agent introduced in the system at various places, as heretofore described. For this purpose any suitable means for heating the gas can be used, and I have indicated a preheater at 68 connected to the discharge line 5I) from pump 49 and controlled by valves B9 and 10.

The temperatures and pressures which can be used in the system cover a Wide range according to the purpose of the operation, i. e. the material undergoing conversion can be heated in heating coil I2 at temperatures varying from 500 to 1500 F., more or less. One of the factors entering into the control choice of the temperature at which the conversion is effected is the step of the process at Which the reacting ragent is to be introduced. In other Words, it may be desirable to subject hydrocarbon oil undergoing conversion to a higher temperature if the gaseous agent is introduced into the process after the hydrocarbon oils have been heated, or to a lower temperature if these reducing agents are introduced in the oil before it is passed through the heating coil.

The pressure must be regulated according to the material treated and product desired, and the.

pressures used may differ Widely in the treatment of two different kinds of hydrocarbons. It will also depend upon the reacting agent used. For instance, a pressure of 3000 lbs. may be suicient in one case, While in another operation it may be necessary to use pressure as high as 5000 lbs. or more. Pressures of this high order are to be distinguished from those customarily employed in cracking since at the temperatures above set forth and in the presence of hydrogen, they result in substantial hydrogenation of the oil for the production of larger quantities of lighter oils containing high percentages of saturated hydrocarbons. Also under these high pressures, the conversion reactions take place While a substantial part of the oil is in the liquid phase, the eiect being a conjoint cracking and hydrogenation of the oil. By the term destructive hydrogenation employed in the claims I intend to refer to this conjoint cracking and hydrogenation of the oil. It is understood, however, that the higher the pressure the speedier the reaction, and that if the desired results can be obtained from the particular material used by operating under a number of diiierent pressures at a range of pressures, it Would be preferable to operate under the higher pressure producing said results.

It is Well understood that the proportion of the reacting agent such as introduced in the system will "vary, and that no gure" canv be accurately determined vWithout l considering together the materialstreated, the products and temperature and pressure conditions with which the process is to be carried out. f Y

In carrying out the process, I' have shown in the apparatus and method illustrated above, a method for separating the sufficiently treated hydrocarbons from the insufficiently treated hydrocarbons by means of vd ephlegmation or frac.- tional condensation.. That isto say that the various constituents of the vapors produced would be separatedaccording to their boiling points. On account o f the complexity of the products made inmyprocess, it may be that several of the materials made vvvhich'are to be withdrawn as finalpr'oducts have approximately the same boiling points so that their separationin this manner is nearly impossible. My invention contemplates the use of any other separating method, such as ltering or separation by means of chemical reagents, fromv which the insuiciently treated material can be further recovered by decantation or precipitation. y

I claim as my invention: v l. A process for the destructive hydrogenation of hydrocarbon oil which comprises passing the oil in admixture with a hydrogen-containing gas through a restricted heating coil and heating the same therein to a conversion temperature under a superatmospheric pressure suicient to effect hydrogenation and liquid phase conversion at the temperature to which the oil is raised, discharging the hot oil and gas into an enlarged reaction Zone maintained at conversion temperature and under suflicient pressure to effect hydrogenation and liquid phase conversion therein, the pressures employed being substantially in excess of 1000 lbs. per square inch, separating the oil into vapors and non-vaporous constituents, and condensing said vapors.

2. A process for the destructive hydrogenation of hydrocarbon oil which comprises passing the oil in admixture with a hydrogen-containing gas through a restricted heating coil and heating the same therein to a conversion temperature under a superatmospheric pressure sufficient to effect hydrogenation and liquid phase conversion at the temperature to which the oil is raised, discharging the hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under suicient pressure to effect hydrogenation and liquid phase conversion therein, introducing additional hydrogen-containing gas into the oil in said reaction zone, separating the oil into vapors and non-vaporous constituents, and condensing said vapors.

3. A process for the destructive hydrogenation of hydrocarbon oil which comprises passing the oil in admixture with a hydrogen-containing gas through a restricted heating coil and heating the same therein toa conversion temperature under a super-atmospheric pressure sufficient to effect hydrogenation and liquid phase conversion at the temperature to which the oil is raised, discharging the hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under suiiicient pressure to effect hydrogenation and liquid phase conversion therein, the pressures employed being substantially in excess of 1000 lbs. per square inch, separating the oil into vapors and non-vaporous constituents, dephlegmating the vapors, returning insuiciently converted constituents to said heating coil and thence to said reaction zone for further tre-:iatment'unde'r conversion and hydrogenating conditions therein and condensing the dephlegmated vapors. Y

4. A process for the destructive hydrogenation of hydrocarbon oil which comprises passing'the oily in' admixture'with' a hydrogen-containing gas' through a restricted heating' coily and heating the` same therein to a conversion temperature undera super-atmospheric pressure suilicientto effect hydrogenation and liquid phase conversion'.V at the'temperature to which the oil is raised, discharging the' hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under suihcient pressure toeffect hydrogenation and liquid phase conversion therein., introducing additional hydrogen-containing gas into the oilv in said reaction zone, separating the oil into vapors and non-vaporous constituents, dephlegmating the vapors, returning insufficiently converted constituents tosaid heating coil and thence to said reaction zone for further treatment` under conversion and hydrogenating conditions therein, and conden'sing the dephlegmated vapors.

5. A' process for the destructive hydrogenation of hydrocarbon oil which comprises passing the oil in admixture with a hydrogen-containinggas through a restricted heating coil and heating the same therein to a conversion temperature under a super-atmospheric pressure sufficient to effect hydrogenation and liquid phase conversion at the temperature to .which the oil is raised, discharging the hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under sufficient pressure to effect hydrogenation and liquid phase conversion therein, withdrawing vaporous reaction products from said reaction zone and introducing the same to a secondary reaction zone, mingling said vaporous products with further quantities of hydrogen-containing gas in said secondary reaction zone, and removing and condensing vapors from said secondary reaction zone.

6. A process for the treatment of hydrocarbon oil for the production of lighter hydrocarbons containing high percentages of saturates which comprises passing the oil in admixture with a hydrogen-containing gas through a restricted heating coil and heating the same therein to a conversion temperature under a super-atmospheric pressure sufficient to effect hydrogenation and conversion at the temperature to which the oil is raised, discharging the hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under suicient pressure to effect hydrogenation and conversion therein, introducing additional hydrogen-containing gas into the oil in said reaction zone, withdrawing vaporous reaction products from said reaction Zone and introducing the same to a secondary reaction zone, mingling said vaporous products With further quantities of hydrogencontaining gas in said secondary reaction zone, and removing and condensing vapors from said secondary reaction zone.

7. A process for the destructive hydrogenation of hydrocarbon oil which comprises heating a flowing stream of the oil to conversion temperature under a pressure sufficient to maintain substantial portions of the oil in liquid condition, discharging the hot oil stream into an enlarged reaction zone maintained under temperature and pressure conditions adequate to effect liquid phase conversion and hydrogenation therein, introducing suicient hydrogen-containing gas directly into the liquid oil in said reaction zone to effect hydrogenation thereof, removing vaporous reaction products from said zone and introducing the same to a secondary reaction zone, mingling the vaporous reaction products in said secondary zone with additional quantities oi' hydrogen-containing gas to effect further hydrogenation thereof, withdrawing vapors from said secondary zone and subjecting the same to condensation.

i 8. A process'for the destructive hydrogenation of hydrocarbon oil which comprises passing the oil in admixture with a hydrogen-containing gas through a restricted heating coil and heating the same'therein to a conversion temperature under a super-atmospheric pressure sufficient to effect hydrogenation and liquid phase conversion at the temperature to which the oil is raised, discharging the hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under sufficient pressure to effect hydrogenation and liquid phase conversion therein, the pressures employed being at least in the neighborhood of about 3000 pounds per square inch, separating the oil into vapors and nonvaporous constituents, and condensing said vapors.

9. A process for the destructive hydrogenation of hydrocarbon oil which comprises passing the oil in admixture with a hydrogen-containing gas through a restricted heating coil and heating the same therein to a conversion temperature under a super-atmospheric pressure sufficient to effect hydrogenation and liquid phase conversion at the temperature to which the oil is raised, discharging the hot oil and gas into an enlarged reaction zone maintained at conversion temperature and under sufficient pressure to effect hyl drogenation and liquid phase conversion therein, the pressures employed being at least in the neighborhood of about 3000 pounds per square inch, separating the oil into vapors and nonvaporous constituents, dephlegmating the vapors, returning insufficiently converted constituents to said heating coil and thence to said reaction zone for further treatment under conversion and hydrogenating conditions therein and condensing the dephlegmated vapors.

10. The process as defined in claim 2 further characterized in that pressures at least of -the order of about 3000 pounds per square inch are employed.

11. The process as defined in claim 4 further characterized in that pressures of 3000 pounds per square inch and above are employed.

CARBON P. DUBBS. 

